Fluoroalkyl siloxane/vinyl copolymer dispersions and pressure-sensitive adhesives having improved solvent resistance prepared therefrom

ABSTRACT

Novel pressure-sensitive adhesives are described which show significant resistance to solvents and working fluids such as jet fuel, hydraulic fluid, de-icing fluid and the like. Adhesive compositions comprise nonaqueous dispersions of copolymers of acrylic monomers prepared in the presence of a vinyl-substituted fluoroalkyl siloxane having the general formula I and a macromonomeric stabilizer. The adhesives prepared from the adhesive compositions exhibit excellent adhesion to glass, aluminum, and low surface-energy materials such as fluoroalkyl siloxane elastomers. 
     The fluoroalkyl siloxane has the formula ##STR1##

This is a division of application Ser. No. 07/947,141 filed Sep. 18,1992 and now U.S. Pat. No. 5,349,004.

FIELD OF THE INVENTION

This invention relates to stable, fluoroalkyl siloxane/vinyl copolymerdispersions which provide pressure-sensitive adhesives having improvedsolvent resistance especially against solvents such as gasoline, jetfuel, hydraulic fluid, and oils. The invention also relates to thesolvent resistant pressure-sensitive adhesives (PSAs) preparedtherefrom.

BACKGROUND OF THE INVENTION

Acrylate pressure-sensitive adhesives are well-known. U.S. Pat. No. Re24,906 (Ulrich), assigned to the assignee of the present case, disclosesalkyl acrylate copolymers which comprise a major amount of alkyl estersof acrylic acid, having from 4 to 14 carbon atoms and which comprise aminor amount (i.e. 3 to 12%, preferably 4 to 8%) of a polar,copolymerizable monomer, such as acrylic acid. Such adhesives are widelypopular, as they are readily available, and provide a good balance oftack, shear, and peel properties on a variety of substrates atrelatively low cost. However, such adhesives can experience poor solventresistance and poor adhesion to low energy surfaces, such aspolyolefins, silicones, and fluorosilicones.

It is well-known that the use of tackifiers in acrylic PSA formulationsenhances the adhesion of the PSAs to low energy surfaces. However, thisincrease in adhesion occurs at the expense of internal strength.

A need has existed for acrylic adhesives having improved solventresistance, especially against such fluids as gasoline, jet fuel,hydraulic fluid, and oils. Two main approaches have been tried toachieve this goal. One approach involved the modification of the acrylicpolymer backbone. The other approach involved the combination of twoelastomers in a hybrid adhesive composition.

EP 0,075,191 (1981), assigned to Daikin Kogyo, describes a solutionpolymer of pentafluoropropyl acrylates which when coated on polyesteryields a tape which experiences less than a 10% adhesion loss whenexposed to oil, gasoline, kerosene, and water. This adhesive requiresexpensive fluorinated acrylate monomers and does not include a secondelastomer as part of the composition.

Fluoroelastomers have been incorporated into adhesive compositions in anattempt to yield adhesives having improved solvent resistance. JP61-31411 (1986), assigned to Suriibondo, describes a radicallypolymerizable composition comprising (meth)acrylate or oligomer thereof,fluoroelastomer, and a curing agent. The cured composition whichdemonstrates improved heat-resistance and oil-resistance can be used asan adhesive and a caulking material. The fluoroelastomers used arevinylidene fluoride/hexafluoropropylene copolymers and the adhesives areultraviolet light (UV) or anaerobically cured. No disclosure is made offluoroalkyl siloxane elastomers. JP 63-117085 (1988), assigned toCentral Glass, discloses a tacky adhesive comprising a copolymer ofvinylidene fluoride and hexafluoroacetone combined with a copolymer of2-ethylhexyl acrylate and vinyl acetate. The adhesive is purported to beweather and oil resistant. Again, no fluoroalkyl siloxane elastomer wasincluded in the composition. EP 0,390,207 (1990), assigned to DaikinIndustries, discloses a vibration damping material obtained bydissolving an amorphous fluorine-containing polymer into acrylic monomerand polymerizing the monomer with or without permitting the resultingpolymer to form an interpenetrating polymer network. The composition isreported to provide excellent damping, solvent resistance, oilresistance, and weathering resistance, however, no pressure sensitiveadhesive properties are taught.

A need thus exists for an inexpensive pressure sensitive adhesive thatis resistant to solvents and adheres well to low energy surfaces, with abalance of tack, adhesion and fluid resistance. We have discovered sucha pressure-sensitive adhesive.

BRIEF DESCRIPTION OF THE INVENTION

We have discovered that the copolymerization of certain acrylic monomerswith a sufficient amount of a fluoroalkyl siloxane elastomer in thepresence of a stabilizer results in a pressure sensitive adhesivecomposition which can be used in forming a PSA having an excellentbalance of tack, adhesion, and solvent resistance. An additional benefitis good adhesion to unprimed fluoroalkyl siloxane elastomers.

The present invention provides an adhesive composition comprising anovel stable, fluoroalkyl siloxane/vinyl nonaqueous copolymer dispersionwhich comprises the polymerization product of a mixture comprising thefollowing components:

(a) about 5 to about 40 parts by weight of a fluoroalkyl siloxane of theformula ##STR2##

wherein:

R⁹ is independently selected from the group consisting of --CH₂ CH₂R_(f) and -R⁷,

R_(f) is a fluoroalkyl group independently selected from the groupconsisting of C_(m) F_(2m-1) and C_(n) F.sub.(2n+1)-q H_(q),

m is an integer ranging from about 1 to about 20;

n is an integer ranging from about 1 to about 20;

q is an integer ranging from about 0 to about 2n;

x is an integer of about 11 or greater;

the fluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_(f) groups;

the fluoroalkylsiloxane comprises at least 1 R⁷ group;

wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independently selectedfrom the group consisting of alkyl groups comprising about 1 to about 12carbon atoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl,fluoroalkyl, and hydrogen; and R⁷ is an organic group comprising atleast two carbon atoms wherein at least 1 olefinic moiety is containedwithin R⁷ ;

wherein the ratio of R⁷ to --CH₂ CH₂ R_(f) is such that the mole percentof the olefinic moiety content contributed by R⁷ of the fluoroalkylsiloxane is between about 0.1 and about 4;

(b) about 60 to about 95 parts by weight of free radically polymerizablemonomer, wherein the free-radically polymerizable monomer comprises:

(i) about 1 to about 20 percent by weight of free radicallypolymerizable polar monomer; and

(ii) about 80 to about 99 percent by weight of free radicallypolymerizable non-polar monomer;

wherein the weight percentages of (i) and (ii) are based upon the totalweight of (i) plus (ii); and wherein the total weight of (a) plus (b)equals 100 parts by weight total;

(c) about 0.1 to about 1 part by weight of a free radical initiatorbased upon 100 parts by weight total of (a) plus (b);

(d) about 2 to about 10 parts by weight of a stabilizer based upon 100parts by weight of total of (a) plus (b) wherein the stabilizer has anumber average molecular weight ranging from about 8000 to about 25,000and wherein the stabilizer is selected from the group consisting of:

(i) a copolymer comprising (A) about 40 to about 60 parts by weight ofmonomer selected from the group consisting of vinyl esters of C₁ to C₈monocarboxylic acids and C₁ to C₁₂ alkyl (meth)acrylates, and (B) about60 to about 40 parts by weight of monomer selected from the groupconsisting of N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide,N-vinylcaprolactam, and mixtures thereof, wherein the copolymercomprises 100 parts by weight total of the monomers of (i)(A) plus(i)(B); and (C) about 0.5 to about 5 weight percent of a chain transferagent based upon the weight of the monomers of (i)(A) plus (i)(B);

(ii) a macromonomer comprising the reaction product of the copolymer of(d)(i), wherein the chain transfer agent selected provides the copolymerwith at least one functional group selected from the group consisting of--NH₂, --COOH, --OH, and combinations thereof, with an endcapping agentselected from the group consisting of isocyanatoethyl methacrylate,alpha, alpha-dimethyl-meta-isopropenyl benzylisocyanate,para(chloromethyl) styrene, vinyl azlactone, glycidyl methacrylate, andmixtures thereof, wherein at least about 95% of the functional group(s)selected from the group consisting of --NH₂, --COOH, --OH, andcombinations thereof, of the copolymer are reacted with the endcappingagent; and

(iii) mixtures thereof; and

(e) about 30 to about 95 percent by weight of an organic solvent basedupon the total weight of (a) plus (b) plus (c) plus (d) plus (e).

Also provided by the present invention are compositions, which upon cureprovide adhesives having even greater resistance to jet fuel, engineoil, hydraulic fluid, brake fluid or similar materials, wherein thecompositions comprise the fluoroalkyl siloxane/vinyl nonaqueousdispersions and a compatible crosslinker.

The novel fluoroalkyl siloxane/vinyl copolymer compositions of thepresent invention provide, upon cure, a balance of fluid resistance andadhesion to glass, aluminum, polyolefins and/or fluoroalkyl siloxaneelastomers. Compared to "all-acrylic" and silicone/acrylic materialsknown in the art, the adhesives of the present invention demonstrateimproved adhesion to fluorosilicone elastomeric materials.

DESCRIPTION OF THE INVENTION Fluoroalkyl Siloxanes

Fluoroalkyl siloxanes of Formula I are useful in the present invention.R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each preferably independentlyselected from the group consisting of alkyl groups comprising about 1 toabout 6 carbon atoms, most preferably about 1 to about 3 carbon atoms.Such fluoroalkyl siloxanes are preferred in that elastomers madetherefrom typically provide optimum solvent and heat resistance and lowtemperature flexibility, whereas elastomers made from fluorosiliconegums comprising larger groups, i.e., C₄ or higher, may tend to havelower solvent and heat resistance and decreased low temperatureflexibility. Furthermore, fluorosilicone gums having such larger groupstypically tend to be more expensive.

R⁷ represents an organic group comprising at least two, typically two tonine carbon atoms, and containing at least one olefinic moiety (i.e., R⁷contains at least 1 ethylenically unsaturated functional group such as avinyl segment). In reference to R⁷, the term "olefinic moiety" refers tocarbon atoms bonded via a double bond(s) and atoms pendant therefrom.Examples of monovalent moieties include but are not limited to --CH═CH₂,--CH═CH--, etc. For example, if R⁷ comprises --CH₂ --CH₂ CH═CH--CH₂--CH═CH₂ there are two olefinic moieties contained therein: --CH═CH--and --CH═CH₂. As another example, when R⁷ comprises --CH₂ --CH₂--CH═CH₂, the olefinic moiety portion is considered to be --CH═CH₂. Asanother example, when R⁷ comprises --CH₂ CO₂ CH═CH₂ the olefinic moietyporiton is considered to be --CH═CH₂. Preferably, the unsaturated bondis terminally-located since terminally-located bonds typically providefor faster cure rates. When R⁷ comprises more than two carbon atoms,non-terminally-located bonds within the group may beethylenically-unsaturated. However, such bonds typically tend to be lessreactive due to the relatively sterically-hindered position of suchbonds. Elastomers formed by curing compositions containing fluoroalkylsiloxanes wherein the R⁷ group comprises more than nine carbon atoms maytend to have lower solvent and heat resistance.

The letter x represents an integer of 11 or greater, typically xrepresents an integer of about 11 to about 5500.

In order to form a copolymer useful as a fluid-resistant adhesive afluoroalkyl siloxane of Formula I should be used wherein the fluoroalkylsiloxane contains 10 or greater --CH₂ CH₂ R_(f) groups in order toprovide a distinct fluoroalkyl siloxane phase to the copolymer,preferably about 2000 to about 3500 --CH₂ CH₂ R_(f) groups, in order toprovide adequate fluid-resistance characteristics to the copolymer whileimproving adhesion to low-energy surfaces (such as silicones,fluoroalkyl-silicones, polyolefins, etc.).

The ratio of R⁷ to --CH₂ CH₂ R_(f) is such that the mole percent ofolefinic or vinyl moiety content is between about 0.1 and about 4,preferably between about 1 and about 2. Compositions wherein theolefinic or vinyl moiety content of the fluoroalkyl siloxane issubstantially lower than these ranges may phase separate to give asmaller number of grafts resulting in a heterogeneous solution. Thosecompositions wherein the olefinic or vinyl moiety content of thefluoroalkyl siloxane is substantially higher than this range may resultin crosslinking of the copolymer.

Fluoroalkyl siloxanes useful in preparing the compositions of thepresent invention typically have a weight average molecular weightbetween about 200,000 and about 700,000, preferably between about250,000 and about 650,000, as determined by gel permeationchromatography. Elastomers cured from compositions made with fluoroalkylsiloxanes having molecular weights substantially below these ranges maytend to have lower tensile strength. Compositions may be made withfluoroalkyl siloxanes having molecular weights higher than these ranges.However, such compositions will typically have higher solutionviscosities, thereby tending to reduce the ease of processability andapplication to the desired substrate. Such high molecular weightfluoroalkyl siloxanes also exhibit reduced compatibility in the presentformulation. The fluorine content of the fluoroalkyl siloxanes useful inthe present invention is typically at least about 20 weight percent,preferably at least about 30 weight percent based upon the weight of thefluoroalkyl siloxanes. If the fluorine content of the fluoroalkylsiloxane is too low the solvent resistance of the resultant elastomermay tend to be reduced, for instance the elastomer may tend to swell toa greater extent.

The number of olefinic moieties contained within the fluoroalkylsiloxane can vary. The weight ratio of the olefinic moieties of thefluoroalkyl siloxane to the total weight of the fluoroalkyl siloxanetypically ranges from about 0.5:99.5 to about 3:97. Preferably, theweight ratio ranges from about 0.5:99.5 to about 1:99.

The fluoroalkyl siloxanes useful in the present invention can beprepared by any known method including, for example, those described inU.S. Pat. Nos. 4,029,629; 4,041,010; 4,529,752; 4,585,848; and4,599,374; all incorporated by reference herein. Examples of fluoroalkylsiloxanes useful in the present invention include but are not limited tothe following fluoroalkyl siloxanes available from the Dow ComingCompany: Silastic® LS-2840, LS-2860, LS-2249U, and LS-2332U. An exampleof a preferred fluoroalkyl siloxane is trifluoropropyl methyl siloxanecontaining 0.1 to 1.0 mole % vinyl sites (i.e., olefinic moietycontent).

Free-radically Polymerizable Monomers

Representative examples of free-radically polymerizable nonpolarmonomers having at least one ethylenically unsaturated polymerizablegroup include but are not limited to those monomers selected from thegroup consisting of alkyl acrylates, preferably monofunctionalunsaturated acrylate esters of primary or secondary alkyl alcohols, themolecules of which comprise from about 1 to about 14 carbon atoms, andmixtures thereof. Examples of specific nonpolar monomers include but arenot limited to those selected from the group consisting of isooctylacrylate, isononyl acrylate, 2-ethylhexyl acrylate, decyl acrylate,dodecyl acrylate, n-butyl acrylate, hexyl acrylate, mixtures thereof,and the like. Preferred nonpolar monomers include those selected fromthe group consisting of isooctyl acrylate, butyl acrylate, 2-ethylhexylacrylate, and mixtures thereof, which monomers provide the best adhesiveproperties.

Representative examples of free-radically polymerizable polar monomershaving at least one ethylenically unsaturated polymerizable group whichare copolymerizable with the nonpolar monomers include strongly polarcopolymerizable monomers including but not limited to those selectedfrom the group consisting of acrylic acid, itaconic acid, hydroxyalkylacrylates, cyanoalkyl acrylates, acrylamides, and substitutedacrylamides, and moderately polar copolymerizable monomers including butnot limited to those selected from the group consisting ofN-vinylpyrrolidone, acrylonitrile, mixtures thereof, and the like.

The preferred monomers include those selected from the group consistingof isooctyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, acrylicacid, itaconic acid, N-vinylpyrrolidone, acrylonitrile, and mixturesthereof. Most preferably, the monomers comprise a mixture of isooctylacrylate, acrylic acid, and N-vinyl pyrrolidone.

The adhesive composition of the invention comprises about 5 to about 40parts by weight fluoroalkyl siloxane and about 60 to about 95 parts byweight free radically polymerizable monomer, preferably about 10 toabout 30 parts by weight fluoroalkyl siloxane and about 70 to about 90pans by weight free radically polymerizable monomer, and most preferablyabout 15 to about 25 parts by weight fluoroalkyl siloxane and about 75to about 85 parts by weight free radically polymerizable monomer, basedupon 100 parts by weight total of fluoroalkyl siloxane and freeradically polymerizable monomer.

The free radically polymerizable monomer typically comprises about 1 toabout 20 percent by weight polar monomer and about 80 to about 99percent by weight nonpolar monomer, preferably about 5 to about 15percent by weight polar monomer and about 85 to about 95 percent byweight nonpolar monomer, most preferably about 8 to about 12 percent byweight polar monomer and about 85 to about 92 percent by weight nonpolarmonomer, based on the total weight of free radically polymerizablemonomer.

Stabilizer

A third component is a stabilizer for the nonaqueous dispersion of theinvention. The stabilizer can comprise a copolymer comprising a) about40 to about 60 parts by weight of monomer selected from the groupconsisting of vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ toC₁₂ alkyl (meth)acrylates, and b) about 60 to about 40 parts by weightof monomer selected from the group consisting of N-vinylpyrrolidone,acrylamide, N,N-dimethylacrylamide, N-vinylcaprolactam, and mixturesthereof wherein the stabilizer comprises 100 parts by weight total ofmonomer, and wherein the stabilizer has a number average molecularweight ranging from about 8,000 to about 25,000. Optionally, the randomcopolymer may be reacted with end-capping monomers (preferably anequimolar amount) to form a macromonomer, the end-capping monomersincluding but not limited to those selected from the group consisting ofisocyanatoethyl methacrylate (IEM) and alpha, alpha-dimethylisopropenylbenzylisocyanate (TMI), vinyl azlactone, para(chloromethyl) styrene,glycidyl methacrylate, and mixtures thereof through --OH, --NH₂, or--COOH functionality or combinations thereof, which may be introduced tothe copolymer through a chain transfer agent. At least about 95% of thefree hydroxyl (--OH), amine (--NH₂), carboxyl (--COOH) groups, orcombinations thereof, preferably at least about 98% of the freehydroxyl, amine, carboxyl groups, or combinations thereof, and mostpreferably about 100% of the free hydroxyl, amine, carboxyl groups, orcombinations thereof, of the copolymer are reacted with end-cappingagent. End-capping introduces ethylenically-unsaturated free-radicallypolymerizable functional groups into the random copolymer such that theend-capped macromonomer can be copolymerized with the fluoroalkylsiloxane and the free-radically polymerizable monomers of the presentinvention as described above. Preferred stabilizers include thoseselected from the group consisting of vinyl acetate/N-vinyl pyrrolidonecopolymer endcapped with IEA and vinyl acetate/N-vinyl pyrrolidonecopolymer endcapped with TMI, and mixtures thereof. Most preferably,vinyl acetate/N-vinylpyrrolidone copolymer endcapped withisocyanatoethyl methacrylate is selected as the stabilizer due to itsease of synthesis and the facility with which it is copolymerized withthe fluoroalkyl siloxane and free-radically polymerizable monomerspresent in the adhesive composition of the present invention.

The copolymer stabilizer can be prepared by combining the desiredmonomers, initiator (such as those discussed below), a chain transferagent such as --OH, --NH₂, or --COOH functional chain transfer agentselected from the group consisting of chain transfer agents whichprovide the copolymer with --OH functionality (e.g., mercaptoethanol),chain transfer agents which provide the copolymer stabilizer with --COOHfunctionality (e.g., mercapto acetic acid), chain transfer agents whichprovide the copolymer stabilizer with --NH₂ functionality (e.g.,mercaptoamine), and mixtures thereof, and a conventional organic solventsuch as ethyl acetate (and/or those discussed below) in a reactionvessel. In cases where the copolymer stabilizer is not to be reactedwith an end-capping agent, a non-functional chain transfer agent can beused such as isooctyl thioglycolate, carbon tetrabromide, and the like.Typically about 20 to about 50 parts by weight of monomer is used.Typically about 0.5 to about 5 weight % of chain transfer agent is usedbased on the weight of the monomer charge. Typically about 80 to about50 parts by weight of solvent is used. Polymerization is conducted underinert atmospheric conditions, with agitation, for about 10 to 24 hours.

A macromonomer stabilizer can be prepared by reacting the copolymer withend-capping agent in the presence of a catalyst such as dibutyl tindilaurate. Typically about 0.03 to about 0.15 weight % of catalyst isused based on the weight of the end-tapping agent. Also about 0.01 toabout 0.1 weight % of a conventional antioxidant such as Irganox™ 1010(available from Ciba-Geigy) based on the monomer charge is included. Thereaction preferably is conducted under inert atmospheric conditions withagitation for about 1 to about 5 hours.

A stable nonaqueous dispersion is obtained only if a stabilizer having anumber average molecular weight ranging from about 8,000 to about 25,000is used. If the molecular weight is too high, the nonaqueous dispersioninitially formed becomes unstable over time and is unusable as acoating. If the stabilizer is not added before polymerization occurs, aseparate fluoroalkyl siloxane and a separate acrylate phase is obtained(i.e., a heterogeneous coating solution). Therefore, the stabilizer isan essential part of the formulation. The stabilizer is typicallyincluded at about 2 to about 10 parts by weight, preferably from about 3to about 6 parts by weight, most preferably about 4 to about 5 parts byweight, based upon 100 parts by weight total of the free-radicallypolymerizable monomer plus fluoroalkyl siloxane.

Initiators

Examples of useful free-radical initiators according to the presentinvention are detailed in Chapters 20 and 21 of Macromolecules, Vol.2,2nd Ed., H. G. Elias, Plenum Press, 1984, New York, incorporated byreference herein. Useful thermal initiators for purposes of the presentinvention include, but are not limited to, those selected from the groupconsisting of the following: azo compounds such as2,2'-azobis-(isobutyronitrile), dimethyl-2,-2'-azo-bis-isobutyrate,azo-bis-(diphenyl methane), 4,4'-azo-bis-(4-cyanopentanoic acid);peroxides such as benzoyl peroxide, cumyl peroxide, tert-butyl peroxide,cyclohexanone peroxide, glutaric acid peroxide, lauroyl peroxide, methylethyl ketone peroxide and hydrogen peroxide; hydroperoxides such astert-butyl hydroperoxide and cumene hydroperoxide; peracids such asperacetic acid and perbenzoic acid; potassium persulfate; peresters suchas diisopropyl percarbonate; and mixtures thereof. Certain of theseinitiators (in particular the peroxides, hydroperoxides, peracids, andperesters) can be induced to decompose by addition of a suitablecatalyst rather than thermally. This redox method of initiation isdescribed in Elias, Chapter 20.

Useful photochemical initiators include but are not limited to thoseselected from the group consisting of benzoin ethers such asdiethoxyacetophenone, oximino-ketones, acylphosphine oxides, diarylketones such as benzophenone and 2-isopropyl thioxanthone, benzil andquinone derivates, and 3-ketocumarines as described by S. P. Pappas, J.Rad. Cur., July 1987, p. 6, incorporated by reference herein.

Preferably, the initiator used comprises a thermally decomposed azo orperoxide compound for solubility reasons and in order to control thereaction rate. Most preferably, the initiator used comprises2,2'-azobis-(isobutyronitrile) for reasons of cost and appropriatedecomposition temperature.

The adhesive composition of the invention comprises about 0.1 to about 1part by weight initiator, preferably about 0.2 to about 0.8 part byweight, most preferably about 0.3 to about 0.5 part by weight, basedupon 100 parts by weight total of fluoroalkyl siloxane and freeradically polymerizable monomer.

Solvent

An organic solvent is utilized in the polymerization process of theinvention in order to decrease the viscosity during the reaction toallow for efficient stirring and heat transfer. The organic solvent usedin the free radical polymerization can be any organic liquid which isessentially inert to the reactants and which will not otherwiseadversely affect the reaction.

Suitable solvents include but are not limited to polar solvents such asthose selected from the group consisting of esters such as ethyl acetateand butyl acetate; ketones such as methyl ethyl ketone, methyl isobutylketone, methyl propyl ketone, acetone; and mixtures thereof.

Other solvent systems are useful as well. Aliphatic and aromatichydrocarbons can be used, although, sometimes they lead to theprecipitation of the vinyl polymeric segment from solution. Hydrocarbonsolvents may be used when admixed with other polar solvents which helpcontrol the molecular weight of the final copolymer.

The solvent utilized in the free radical polymerization, may be anysubstance which is liquid in a temperature range of about -10° C. toabout 110° C., does not interfere with the energy source or catalystused to dissociate the initiator to form free radicals, is inert to thereactants and product and will not otherwise adversely affect thereaction. The organic solvent selected is capable of dissolving thefluoroalkyl siloxane, monomer, stabilizer, and initiator to form amixture. The amount of solvent used is generally about 30 to about 95percent by weight based on the total weight of the reactants (i.e.,fluoroalkyl siloxane, polar monomer, non-polar monomer, initiator,stabilizer) plus solvent. Preferably, the amount of solvent utilizedranges from about 40 to about 50 percent by weight, most preferablyabout 35 to 40 percent by weight based upon the total weight of thereactants plus solvent in order to obtain fast reaction times and highmolecular weight of the polymer at appropriate product viscosities.

Methods of Polymerization

The homolytic decomposition of the initiator used in the presentinvention to form free radicals can be induced by heat energy(thermolysis), light energy (photolysis), or the addition of a suitablecatalyst. The decomposition rate of the initiator during thermolysisdepends upon the chemical nature of the initiator, the reactiontemperature, and the solvent used. The decomposition rate of theinitiator during photolysis depends mainly upon the chemical nature ofthe initiator and the intensity and wavelength of the radiationutilized.

Light energy can be supplied to induce the homolytic decomposition ofthe initiator by means of visible or ultraviolet sources including lowintensity fluorescent black light lamps, medium pressure mercury arclamps, and germicidal mercury lamps. The selection of a preferred lightenergy source will depend upon the chosen photoinitator.

The decomposition of the initiator can also be accomplished by using asuitable catalyst. Catalyst induced initiator decomposition involves anelectron transfer mechanism resulting in a reduction-oxidation (redox)reaction. Initiators such as peroxides and hydroperoxides are moresusceptible to this kind of decomposition. Catalysts useful in inducingthe homolytic decomposition of the initiator include, but are notlimited to those selected from the group consisting of amines and metalions used in combination with peroxide or hydroperoxide initiators andbisulfite or mercapto compounds used in combination with persulphateinitiators.

The preferred method of initiation is thermolysis which can be readilyemployed in standard reactors. Thermolysis also provides for ease ofcontrol of the reaction rate and exotherm.

The free-radically polymerizable monomers, the initiator, thestabilizer, the fluoroalkyl siloxane, and the solvent employed arecharged into an appropriate reaction vessel in order to form a mixture.If photolysis is conducted to decompose the initiator, the reactants andany solvent employed are charged into an energy source transparentvessel and therein subjected to the energy source. If the energy sourceis ultraviolet light radiation, a suitable ultraviolet light-transparentvessel is utilized.

If thermolysis is used to decompose the initiator, the reactants andsolvent employed are charged into a suitable glass or metal reactor, andtherein subjected to the thermal energy source. If catalysis is used todecompose the initiator, a glass or metal reactor can also be utilized.

The reaction is preferably conducted in a vessel with agitation topermit uniform exposure of the reactants to the energy source. Whilemost of the reactions have been conducted by employing a batch process,it is possible to utilize the same technology in a continuouspolymerization operation.

Reaction times on the order of about 1 to about 40 hours have been foundtypical, depending upon the amount and type of solvent used, the amountand type of initiator used, temperatures or photolytic energy supplied,and the nature of the free radically polymerizable monomers.

Optional Additives

The adhesive composition of the invention can be blended with one ormore compatible modifiers in order to optimize physical properties. Forexample, it may be desirable to include an additive selected from thegroup consisting of pigments, extenders, conducting material, variouspolymeric additives, and mixtures thereof. It is theorized that thecopolymer contained in the dispersion made in the practice of thepresent invention can be recovered by standard procedures such asevaporation of solvent, or precipitation after polymerization into wateror a suitable organic solvent such as methanol, hexane, etc. It istheorized that standard extraction techniques may also be used ifdesired. It is also theorized that the copolymer may also be taken orinverted into a different solvent either by a solvent exchange process,e.g. by adding a higher boiling solvent and then distilling out the lowboiling solvent or by azeotropic distillation, a technique well known inthe art.

The fluid-resistant pressure-sensitive adhesive composition of thepresent invention may comprise the defined copolymer dispersion alone ormay, we theorize, comprise the copolymer dispersion blended with acompatible homopolymer, copolymer, etc. The low percentage offluoroalkyl siloxane polymeric segment contained in the copolymerdispersion makes this fluoroalkyl siloxane/vinyl copolymer dispersionreadily compatible, for purposes of blending, with other polymers whosecomposition is similar to the vinyl polymeric segment. In addition,there are several pairs of dissimilar polymers that yield compatibleblends due to specific interactions as described by S. Krause in PolymerBlends, Academic Press, New York, 1978, incorporated by referenceherein.

The fluoroalkyl siloxane/vinyl copolymer dispersions of the presentinvention can be used for a variety of applications, such as preparingfluid-resistant adhesives and sealants, form-in-place multipurposegasketing compounds, etc. The fluoroalkyl siloxane/vinyl copolymerstable nonaqueous dispersions are particularly useful for making afluid-resistant pressure-sensitive adhesive.

A dispersion composition capable of providing a PSA having even greatersolvent resistance can be prepared by adding a crosslinker to thedispersion. Thus, a dispersion composition capable of forming adhesiveshaving even greater fluid resistance can be made by adding from about0.1% to about 0.5% by weight of a crosslinker into the stablefluoroalkyl siloxane/vinyl copolymer nonaqueous dispersion, based uponthe percent solids (i.e., fluoroalkyl siloxane, free-radicallypolymerizable monomer, initiator, and stabilizer). Examples of usefulcrosslinkers include but are not limited to thermally-activated,moisture-activated, and ultraviolet radiation (UV) activatedcrosslinkers. Examples of thermally-activated crosslinkers include butare not limited to those selected from the group consisting ofmultifunctional aziridine amides such asN,N'-bis-1,2-propyleneterephthalamide, metal complexes such as aluminumacetylacetonate, metal ions such as Zn²⁺, Zr²⁺, and Ni²⁺, which can beprovided in the form of soluble metal salts, and isocyanates such asH-12MDI (4,4'-methylene-bis-[cyclohexylisocyanate]). Examples ofmoisture-activated crosslinkers include but are not limited to thoseselected from the group consisting of silanes such astrimethoxysilylpropyl methacrylate (Tris), amino silane, epoxy silane,and mixtures thereof. Examples of UV-activated crosslinkers include butare not limited to those selected from the group consisting of triazinesas described in U.S. Pat. No. 4,330,590 (Vesley, 3M) and U.S. Pat. No.4,329,384 (Vesley et al., 3M) and copolymerizable aromatic ketonemonomers as described in U.S. Pat. No. 4,737,559 and U.S. Pat. No.4,847,137 (Kellen et al., 3M), all of which are incorporated byreference herein.

The preferred weight ratio of vinyl polymeric segment to fluoroalkylsiloxane polymeric segment of the present copolymer dispersion rangesfrom about 60:40 to about 95:5, in order to allow for a wide range offluid-resistant performance while still maintaining good adhesion tovarious substrates.

For improved fluid-resistant properties the copolymer can be crosslinkedby standard methods well known in the art, such as radiation curing(electron beam or ultraviolet light) or chemical curing.

The above-described nonaqueous dispersion can be coated onto substratessuch as silicone coated paper liner, polyethylene terephthalate film,fluorosilicone backing, etc., by any conventional coating means such asMeyer rod, gravure, ruling mills, etc. The coated substrates aretypically dried and cured by heating to a temperature of about 65° C.for about 15 to about 30 minutes.

    ______________________________________                                        Abbreviations and Tradenames                                                  ______________________________________                                        VAc        Vinyl acetate                                                      NVP        N-vinyl pyrrolidone                                                LPM        liter-per-minute                                                   IEM        isocyanate ethyl methacrylate                                      DBTL       Dibutyl tin dilaurate                                              MEK        Methyl ethyl ketone                                                IOA        Isooctyl acrylate                                                  AA         Acrylic acid                                                       Hrs        Hours                                                              Alum.      Aluminum                                                           FSi        Fluorosilicone                                                     64ZO ™  2,2'-azobis(isobutyronitrile) available from                                  duPont                                                             Irganox ™ 1010                                                                        pentaerythritol, tetrakis [3-(3,5-di-tert-butyl-4-                            hydroxyphenyl)proprionate]antioxidant,                                        from Ciba Geigy Company                                            LS-2860    A fluoroalkyl silicone elastomer available                                    from Dow Corning Co. (weight average                                          molecular weight of approximately 490,000,                                    olefinic moiety content of about 0.6 mole %)                       Ex.        Example                                                            ______________________________________                                    

TEST METHODS Molecular Weight Determination

The characterization of the molecular weight distribution of thepolymers described herein has been by conventional gel permeationchromatography (GPC).

A Hewlett-Packard Model 1084B high performance liquid chromatographequipped with Styragel™ columns was used. The system was calibratedusing polystyrene standards. All molecular weight averages arepolystyrene equivalent molecular weights. The molecular weight averageswere calculated according to accepted practices. GPC test methods arefurther explained in "Modern Size Exclusion Liquid Chromatography",Practice of Gel Permeation Chromatography, John Wiley, New York, 1979,incorporated by reference herein.

Peel Adhesion (Reference: ASTM D3330-78 PSTC-1 (11/75))

Peel adhesion is the force required to remove a coated flexible sheetmaterial from a test panel measured at a specific angle and rate ofremoval. In the examples, this force is expressed in Newtons per 100 mm(N/100 mm) width of coated sheet. The procedure followed is:

1. A 12.5 mm width of the coated sheet is applied to the horizontalsurface of a clean glass or aluminum test plate with at least 12.7lineal cm in firm contact. A hard robber roller is used to apply thestrip.

2. The free end of the coated strip is doubled back nearly touchingitself so the angle of removal will be 180°. The free end is attached tothe adhesion tester scale.

3. The glass test plate is clamped in the jaws of a tensile testingmachine which is capable of moving the plate away from the scale at aconstant rate of 2.3 meters per minute.

4. The scale reading in Newtons is recorded as the tape is peeled fromthe glass surface. The data is reported as the range of numbers observedduring the test.

EXAMPLES

The following non-limiting examples further illustrate the presentinvention. All parts, percentages, ratios, etc. in the examples and therest of the specification are by weight unless otherwise indicated.

Example 1 Synthesis of VAc/NVP Copolymer Stabilizer

14.0 g NVP, 10.84 g VAc, 0.8 g mercaptoethanol, 0.12 g VAZO™ 64 and 41.4g ethyl acetate were charged into a 130 ml. amber bottle. The resultingsolution was purged with N₂ for 2 minutes at the rate of 1 LPM. Thebottle was sealed and tumbled in a constant temperature bath at 65° C.for 17 hours.

Example 2 Capping of VAc/NVP Copolymer with IEM to Prepare MacromonomerStabilizer

To the polymer solution obtained in Example 1, 1.2 g IEM, 0.25 g DBTLand approximately 0.13 g of Irganox™ 1010 was added and the resultingsolution was purged with N₂ for 2 minutes at the rate of 1 LPM. Thebottle was sealed and tumbled in a constant temperature bath at 55° C.for 3 hours. IR analysis showed complete capping.

Examples 3-13

The fluoroalkyl siloxane LS-2860 (available from Dow CorningCorporation) was charged at 20 to 30% into a series of bottlescontaining MEK and dissolved in order to form thick syrups. To theresulting thick syrups were added various ratios of IOA/AA or IOA/AA/NVPmonomers. In addition, VAc/NVP capped macromonomer or untapped copolymerstabilizer was added to the syrups. The syrups were then diluted to 40%solids with MEK containing VAZO™ 64 initiator. The resulting solutionswere purged with N₂ for 2 minutes at the rate of 1 LPM and tumbled for20-24 hours in a constant temperature bath at 65 ° C. Specifics of theseformulations are presented in Table I. Percentage solids showed 97-99%conversion.

Control Example A

The procedure of Examples 3-13 was followed except that stabilizer wasnot included. Specifics of the formulation are presented in Table I.Percentage solids showed 97-99% conversion.

Control Example B

The procedure of Examples 3-13 was followed except that fluoroalkylsiloxane was not included. Specifics of the formulation are presented inTable I. Percentage solids showed 97-99% conversion.

                                      TABLE I                                     __________________________________________________________________________                          g VAC/NVP                                               Example                                                                            LS-2860                                                                            g IOA                                                                             g AA                                                                              g NVP                                                                             Stabilizer                                                                           g MEK                                                                              g VAZO-64                                   __________________________________________________________________________    Control                                                                            12.0 25.2                                                                              2.8 --  --     61.0 0.24                                        Ex. A                                                                         3    12.0 25.2                                                                              2.9 --  4.0.sup.2                                                                            61.0 0.24                                        4    12.0 26.0                                                                              2.0 --  4.0.sup.2                                                                            60.0 0.24                                        5    12.0 26.6                                                                              1.4 --  4.0.sup.2                                                                            65.0 0.24                                        6    6.0  21.6                                                                              0.96                                                                              1.44                                                                              3.0.sup.2                                                                            46.0 0.18                                        7    6.0  22.1                                                                              0.50                                                                              1.44                                                                              3.0.sup.2                                                                            47.0 0.18                                        8    6.0  21.6                                                                              1.44                                                                              0.50                                                                              3.0.sup.2                                                                            46.0 0.18                                        9    6.0  21.1                                                                              1.44                                                                              1.44                                                                              3.0.sup.2                                                                            46.0 0.18                                        10   6.0  21.6                                                                              1.44                                                                              0.96                                                                              3.0.sup.2                                                                            45.0 0.18                                        11   6.0  20.6                                                                              1.92                                                                              1.63                                                                              3.0.sup.2                                                                            45.0 0.18                                        12   6.0  20.2                                                                              2.40                                                                              1.44                                                                              3.0.sup.2                                                                            45.0 0.18                                        13   6.0  21.6                                                                              1.44                                                                              0.96                                                                              3.0.sup.1                                                                            45.0 0.18                                        Control                                                                            --   45.0                                                                              3.0  2.0                                                                              --     70.0 0.24                                        Ex. B                                                                         __________________________________________________________________________     .sup.1 Uncapped VAc/NVP copolymer prepared according to Example 1.            .sup.2 Capped VAc/NVP macromonomer prepared according to Example 2.      

Control Example A yielded phase separated material, and was thusrejected for further evaluation.

The purpose of Example 13 was to determine the effect of uncappedVAc/NVP stabilizer on polymerization. A homogeneous solution wasobtained after the polymerization whether capped or uncapped VAc/NVPstabilizer was used.

Example 14

The procedure of Examples 3-13 was repeated. The charges were asfollows: fluoroalkyl silicone LS-2860 (5.0 g), n-butyl acrylate (18.0g), acrylic acid (1.2 g), N-vinyl pyrrolidone (0.8 g), IEM-capped vinylacetate/N-vinyl pyrrolidone (2.5 g @ 36.9% solids), Vazo™ 64 (0.15 g),and methyl ethyl ketone (37.5 g). Percentage solids showed 97-99%conversion.

Example 15

The procedure of Examples 3-13 was repeated. The charges were asfollows: fluoroalkyl silicone LS-2860 (5.0 g), 2-ethylhexyl acrylate(18.0 g), acrylic acid (1.2 g), N-vinyl pyrrolidone (0.8 g), IEM-cappedVAc/NVP (2.5 g 36.9% solids), Vazo™ 64 (0.15 g) and methyl ethyl ketone(37.5 g). Percentage solids showed 97-99% conversion.

Example 16

The procedure of Examples 3-13 was repeated. The charges were asfollows: fluoroalkyl silicone LS-2860 (5.0 g), ethyl acrylate (18.0 g),acrylic acid (1.2 g), N-vinyl pyrrolidone (0.8 g), IEM-capped VAc/NVP(2.5 g @ 36.9% solids), Vazo™ 64 (0.15 g), and methyl ethyl ketone (37.5g). Percentage solids showed 97-99% conversion.

Example 17

The procedure of Examples 3-13 was repeated. The charges were asfollows: fluoroalkyl silicone LS-2860 (5.0 g), isooctyl acrylate (18.0g), acrylic acid (1.2 g), N-vinyl pyrrolidone (0.8 g), IEM-cappedVAc/NVP (2.5 g 36.9% solids), Vazo™ 64 (0.15 g) and methyl ethyl ketone(37.5 g). Percentage solids showed 97-99% conversion.

Tape Preparation and Adhesion Tests

The approximately 40% solids solutions of Examples 3-12 and 14-17 werecoated on corona-treated polyethylene terephthalate films after adding0.3 weight percent bisamide (N,N'-bis-1,2-propyleneterephthalamide)curing agent to each solution based upon the weight of the solution. Thecoated films were dried and cured in an air-forced oven at 65° C. for 15to 20 minutes and stored in a construct-temperature andconstant-humidity room for 24 hours. Results for adhesion to glass,aluminum and fluorosilicone backing are shown in Table II. The datacontained in Table II demonstrates that the adhesive of the inventionexhibits good to excellent adhesion to glass, aluminum, andfluorosilicone backing material when compared to Control B (which doesnot contain a fluorosiloxane polymeric segment). Control Example B(IOA/AA/NVP) shows adhesion of 9.8N/dm to fluorosilicone backingmaterial, compared to 44N/din for the adhesive of Example 17.

Solvent-Resistance Tests

The approximately 40% solids solutions of Examples 9, 10, 14, 15, 17,and Control Example B were coated onto corona-treated polyethyleneterephthalate film after adding 0.3 weight percent bisamide curing agentto each solution, based upon tile weight of the solution. One-half inchstrips (1.27 cm) of the PET tapes coated with adhesive were laminated toaluminum plates then aged at constant temperature and humidity as above.Adhesion to aluminum was determined as above for half of the samples,and the other half were soaked in various fluids, as noted in Table IIIfor three hours then tested for peel adhesion. Comparative resultsreported in Table III show that the fluorosiloxane-containing adhesivesof the present invention retain superior adhesion to aluminum aftersoaking in fluids as described. After soaking in JP-4 jet fuel(available from the Shell Oil Company) for 3 hours, Control Example Bshowed adhesion loss of more than 80%, while Example 17 showed adhesionloss of only 3%. Tapes soaked in hydraulic fluid or engine oil did notleave any residue on removal from aluminum test panels while tapessoaked in JP-4 jet fuel or deicing fluid left only trace amounts ofresidue on removal from the panels.

The deicing fluid used was 02143 TEXACO Aircraft De-Icing Fluid WD-30,available from the TEXACO Lubricants Company, Houston, Tex. WD-30comprises 80 to 95% 1,2-ethanediol and 4 to 11% deionized water. Thehydraulic fluid used was 01537 Aircraft Hydraulic Oil 15, available fromTexaco, Inc. The hydraulic fluid comprises 65 to 80% petroleum oil, 20to 35% methacrylate polymer, less than 1% triaryl phosphate, and lessthan 1% ditertiarybutyl phenol. The engine oil used was Turbo Oil 2380,which is a synthetic aviation lubricant, available from EXXON Company,U.S.A. The engine oil comprises 100% polyol esters and proprietaryadditives. JP-4 jet fuel refers to an industry standard jet fuel whichis available commercially from a number of sources.

                  TABLE II                                                        ______________________________________                                                 Adhesion* to                                                                              Adhesion* to                                                                             Adhesion* to                                           Glass       Aluminum   Fluorosilicone                                Example  (N/dm)      (N/dm)     (N/dm)                                        ______________________________________                                         3       8.8         61.4       21.6                                           4       25.1        30.4       40.7                                           5       32.6        41.1       36.3                                           6       56.3        55.9       34.3                                           7       36.5        41.1       30.6                                           8       58.1        53.0       36.7                                           9       55.9        52.4       32.3                                          10       56.8        59.0       41.8                                          11       --          41.6       --                                            12       --          16.7       --                                            14       59.4        55.2       56.2                                          15       53.0        49.7       40.3                                          16       7.5         2.4        4.8                                           17       49.0        41.4       44.0                                          Control Ex.                                                                            70.3        71.2       9.8                                           ______________________________________                                         *Adhesions are measured at 2.3 m/min. (180° peel)                 

                                      TABLE III                                   __________________________________________________________________________                     Adhesion to Aluminum After*                                  Adhesion Before* Soaking in a Fluid for 3 Hrs                                 Soaking in a Fluid                                                                             (N/dm)                                                       (N/dm)                  De-Icing                                                                           Hydraulic                                                                           Engine                                     Ex.      Glass                                                                             Alum.                                                                             Jet Fuel                                                                             Fluid                                                                              Fluid Oil                                        __________________________________________________________________________     9       55.9                                                                              52.4                                                                              46.9   44.7 51.9  52.6                                                        (No residue)                                                                         (15%)                                                                              (0.8%)                                                                              (No loss)                                                   (10% loss)                                                   10       56.8                                                                              59.0                                                                              47.5   46.9 55.2  54.8                                                        (19.4% loss)                                                                         (20%)                                                                              (6.0%)                                                                              (7%)                                       14       59.4                                                                              55.2                                                                              51.3   --   --    --                                                          (7% loss,                                                                     residue)                                                     15       53.0                                                                              49.7                                                                              45.5   --   --    --                                                          (8.5%)                                                       17       49.0                                                                              41.4                                                                              40.1   --   --    --                                                          (3.1%)                                                       B        70.3                                                                              71.2                                                                              13.2   18.7 --    --                                         (Control)        (82%)  (75%)                                                 (IOA/AA/NVP)                                                                  __________________________________________________________________________     ()Shows the loss in adhesion after the tape laminated on aluminum has bee     soaked in a fluid for 3 hours                                                 *Adhesions are measured at 2.3 m/min. (180° peel)                 

While this invention has been described in connection with specificembodiments, it should be understood that it is capable of furthermodification. The claims herein are intended to cover those variationswhich one skilled in the art would recognize as the chemical equivalentof what has been described here.

What is claimed:
 1. An adhesive comprising a cured adhesive composition,wherein the adhesive composition comprises:a dispersion comprising thepolymerization product of a mixture comprising: (a) about 5 to about 40parts by weight of a fluoroalkyl siloxane of the formula ##STR3##wherein: R⁹ is independently selected from the group consisting of --CH₂CH₂ R_(f) and -R⁷, R_(f) is a fluoroalkyl group independently selectedfrom the group consisting of C_(m) F_(2m-1) and C_(n) F.sub.(2n+1)-qH_(q), m is an integer ranging from about 1 to about 20; n is an integerranging from about 1 to about 20; q is an integer ranging from about 0to about 2n; x is an integer of about 11 or greater; thefluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_(f) groups; thefluoroalkylsiloxane comprises at least 1 R⁷ group; wherein R¹, R², R³,R⁴, R⁵, R⁶, and R⁸ are each independently selected from the groupconsisting of alkyl groups comprising about 1 to about 12 carbon atoms,aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, andhydrogen; and R⁷ is an organic group having at least two carbon atomswherein at least 1 olefinic moiety is contained within R⁷ ; wherein theratio of R⁷ to --CH₂ CH₂ R_(f) is such that the mole percent of theolefinic moiety content contributed by R⁷ of the fluoroalkyl siloxane isbetween about 0.1 and about 4; (b) about 60 to about 95 parts by weightof free radically polymerizable monomer, wherein the free-radicallypolymerizable monomer comprises:(i) about 1 to about 20 percent byweight of free radically polymerizable polar monomer; and (ii) about 80to about 99 percent by weight of free radically polymerizable non-polarmonomer; wherein the weight percentages of (i) and (ii) are based uponthe total weight of (i) plus (ii); and wherein the total weight of (a)plus (b) equals 100 parts by weight total; (c) about 0.1 to about 1 partby weight of a free radical initiator based upon 100 parts by weighttotal of (a) plus (b); (d) about 2 to about 10 parts by weight of astabilizer based upon 100 parts by weight of total of (a) plus (b)wherein said stabilizer has a number average molecular weight rangingfrom about 8000 to about 25,000 and wherein said stabilizer is selectedfrom the group consisting of:(i) a copolymer comprising (A) about 40 toabout 60 parts by weight of monomer selected from the group consistingof vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl(meth)acrylates, and (B) about 60 to about 40 parts by weight of monomerselected from the group consisting of N-vinylpyrrolidone, acrylamide,N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof whereinsaid copolymer stabilizer comprises 100 parts by weight total of themonomers of (i)(A) plus (i)(B); and (C) about 0.5 to about 5 weightpercent of a chain transfer agent based upon the weight of the monomersof (i)(A) plus (i)(B); (ii) a macromonomer comprising the reactionproduct of the copolymer of (d)(i) wherein said chain transfer agentselected provides said copolymer with at least one functional groupselected from the group consisting of --NH₂, --COOH, --OH, andcombinations thereof, with an endcapping agent selected from the groupconsisting of isocyanatoethyl methacrylate, alpha,alpha-dimethyl-meta-isopropenyl benzylisocyanate, vinyl azlactone,para(chloromethyl) styrene, glycidyl methacrylate, and mixtures thereof,wherein at least about 95% of the functional groups selected from thegroup consisting of --NH₂, --COOH, --OH, and combinations thereof, ofthe copolymer are reacted with the endcapping agent; and (iii) mixturesthereof; and (e) about 30 to about 95 percent by weight of an organicsolvent based upon the total weight of (a) plus (b) plus (c) plus (d)plus (e).
 2. An adhesive comprising a cured adhesive composition,wherein the adhesive composition comprises:a dispersion comprising thepolymerization product of a mixture comprising: (a) about 10 to about 30parts by weight of a fluoroalkyl siloxane of the formula ##STR4##wherein: R⁹ is independently selected from the group consisting of --CH₂CH₂ R_(f) and -R⁷, R_(f) is a fluoroalkyl group independently selectedfrom the group consisting of C_(m) F_(2m-1) and C_(n) F.sub.(2n+1)-qH_(q), m is an integer ranging from about 1 to about 20; n is an integerranging from about 1 to about 20; q is an integer ranging from about 0to about 2n; x is an integer of about 11 or greater; thefluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_(f) groups; thefluoroalkylsiloxane comprises at least 1 R⁷ group; wherein R¹, R², R³,R⁴, R⁵, R⁶, and R⁸ are each independently selected from the groupconsisting of alkyl groups comprising about 1 to about 12 carbon atoms,aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, andhydrogen; and R⁷ is an organic group having at least two carbon atomswherein at least 1 olefinic moiety is contained within R⁷ ; wherein theratio of R⁷ to --CH₂ CH₂ R_(f) is such that the mole percent of theolefinic moiety content contributed by R⁷ of the fluoroalkyl siloxane isbetween about: 0.1 and about 4; (b) about 70 to about 90 parts by weightof free-radically polymerizable monomer, wherein said free-radicallypolymerizable monomer comprises:(i) about 5 to about 15 percent byweight of free-radically polymerizable polar monomer; and (ii) about 85to about 95 percent by weight of free-radically polymerizable non-polarmonomer; wherein said weight percentages of (i) and (ii) are based uponthe total weight of (i) plus (ii); and wherein the total weight of (a)plus (b) equals 100 parts by weight total; (c) about 0.2 to about 0.8parts by weight of a free radical initiator based upon 100 parts byweight total of (a) plus (b); (d) about 3 to about 6 parts by weight ofa stabilizer based upon 100 parts by weight of total of (a) plus (b)wherein said stabilizer has a number average molecular weight rangingfrom about 8000 to about 25,000 and wherein said stabilizer is selectedfrom the group consisting of:(i) a copolymer comprising (A) about 40 toabout 60 parts by weight of monomer selected from the group consistingof vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl(meth)acrylates, and (B) about 60 to about 40 parts by weight of monomerselected from the group consisting of N-vinylpyrrolidone, acrylamide,N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof whereinsaid copolymer stabilizer comprises 100 parts by weight total of themonomer of (i)(A) plus (i)(B); and (C) about 0.5 to about 5 weightpercent of a chain transfer agent based upon the weight of the monomersof (i)(A) plus (i)(B); (ii) a macromonomer comprising a reaction productof the copolymer of (d)(i) wherein said chain transfer agent selectedprovides said copolymer with at least one functional group selected fromthe group consisting of --NH₂, --COOH, --OH, and combinations thereof,with an endcapping agent selected from the group consisting ofisocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenylbenzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidylmethacrylate, and mixtures thereof, wherein at least about 95% of thefunctional group(s) selected from the group consisting of --NH₂, --COOH,--OH, and combinations thereof, of the copolymer are reacted the withend-tapping agent; and (iii) mixtures thereof; and (e) about 40 to about50 percent by weight of an organic solvent based upon the total weightof (a) plus (b) plus (c) plus (d) plus (e).
 3. An adhesive comprising acured adhesive composition, wherein the adhesive composition comprises:adispersion comprising the polymerization product of a mixturecomprising: (a) about 15 to about 25 parts by weight of a fluoroalkylsiloxane of the formula ##STR5## wherein: R⁹ is independently selectedfrom the group consisting of --CH₂ CH₂ R_(f) and -R⁷, R_(f) is afluoroalkyl group independently selected from the group consisting ofC_(m) F_(2m-1) and C_(n) F.sub.(2n+1)-q H_(q), m is an integer rangingfrom about 1 to about 20; n is an integer ranging from about 1 to about20; q is an integer ranging from about 0 to about 2n; x is an integer ofabout 11 or greater; the fluoroalkylsiloxane comprises 10 or greater--CH₂ CH₂ R_(f) groups; the fluoroalkylsiloxane comprises at least 1 R⁷group; wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independentlyselected from the group consisting of alkyl groups comprising about 1 toabout 12 carbon atoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl,fluoroalkyl, and hydrogen; and R⁷ is an organic group having at leasttwo carbon atoms wherein at least 1 olefinic moiety is contained withinR⁷ ; wherein the ratio of R⁷ to --CH₂ CH₂ R_(f) is such that the molepercent of the olefinic moiety content contributed by R⁷ of thefluoroalkyl siloxane is between about 0.1 and about 2; and wherein saidfluoroalkyl siloxane has a weight average molecular weight of about250,000 to about 600,000, and a fluorine content of at least about 30weight percent; (b) about 75 to about 85 parts by weight offree-radically polymerizable monomer, wherein said free-radicallypolymerizable monomer comprises:(i) about 8 to about 12 percent byweight of free-radically polymerizable polar monomer; and (ii) about 85to about 92 percent by weight of free-radically polymerizable non-polarmonomer; wherein said weight percentages of (i) and (ii) are based uponthe total weight of (i) plus (ii); and wherein the total weight of (a)plus (b) equals 100 parts by weight total; (c) about 0.3 to about 0.5parts by weight of a free radical initiator based upon 100 parts byweight total of (a) plus (b); (d) about 4 to about 5 parts by weight ofa stabilizer based upon 100 parts by weight of total of (a) plus (b)wherein said stabilizer has a number average molecular weight rangingfrom about 8000 to about 25,000 and wherein said stabilizer is selectedfrom the group consisting of:(i) a copolymer comprising (A) about 40 toabout 60 parts by weight of monomer selected from the group consistingof vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl(meth)acrylates, and (B) about 60 to about 40 parts by weight of monomerselected from the group consisting of N-vinylpyrrolidone, acrylamide,N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof whereinsaid copolymer comprises 100 parts by weight total of the monomers of(i)(A) plus (i)(B); and (C) about 0.5 to about 5 weight percent of achain transfer agent based upon the weight of the monomers of (i)(A)plus (i)(B); (ii) a macromonomer comprising the reaction product of thecopolymer of (d)(i) wherein said chain transfer agent selected providessaid copolymer with at least one functional group selected from thegroup consisting of --NH₂, --COOH, --OH, and combinations thereof, withan endcapping agent selected from the group consisting ofisocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenylbenzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidylmethacrylate, and mixtures thereof, such that at least about 95% of thefunctional group(s) selected from the group consisting of --NH₂, --COOH,--OH, and combinations thereof, of the copolymer are reacted with theendcapping agent; and (iii) mixtures thereof; and (e) about 35 to about40 percent by weight of an organic solvent based upon the total weightof (a) plus (b) plus (c) plus (d) plus (e).
 4. An adhesive comprising acured adhesive composition wherein the adhesive composition comprises:adispersion comprising the polymerization product of a mixturecomprising: (a) about 5 to about 40 parts by weight of a fluoroalkylsiloxane of the formula ##STR6## wherein: R⁹ is independently selectedfrom the group consisting of --CH₂ CH₂ R_(f) and -R⁷, R_(f) is afluoroalkyl group independently selected from the group consisting ofC_(m) F_(2m-1) and C_(n) F.sub.(2n+1)-q H_(q), m is an integer rangingfrom about 1 to about 20; n is an integer ranging from about 1 to about20; q is an integer ranging from about 0 to about 2n; x is an integer ofabout 11 or greater; the fluoroalkylsiloxane comprises 10 or greater--CH₂ CH₂ R_(f) groups; the fluoroalkylsiloxane comprises at least 1 R⁷group; wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independentlyselected from the group consisting of alkyl groups comprising about 1 toabout 12 carbon atoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl,fluoroalkyl, and hydrogen; and R⁷ is an organic group having at leasttwo carbon atoms wherein at least 1 olefinic moiety is contained withinR⁷ ; wherein the ratio of R⁷ to --CH₂ CH₂ R_(f) is such that the molepercent of the olefinic moiety content contributed by R⁷ of thefluoroalkyl siloxane is between about 0.1 and about 4; (b) about 60 toabout 95 parts by weight of free radically polymerizable monomer,wherein the free-radically polymerizable monomer comprises:(i) about 1to about 20 percent by weight of free radically polymerizable polarmonomer; and (ii) about 80 to about 99 percent by weight of freeradically polymerizable non-polar monomer; wherein the weightpercentages of (i) and (ii) are based upon the total weight of (i) plus(ii); and wherein the total weight of (a) plus (b) equals 100 parts byweight total; (c) about 0.1 to about 1 part by weight of a free radicalinitiator based upon 100 parts by weight total of (a) plus (b); (d)about 2 to about 10 parts by weight of a stabilizer based upon 100 partsby weight of total of (a) plus (b) wherein said stabilizer has a numberaverage molecular weight ranging from about 8000 to about 25,000 andwherein said stabilizer is selected from the group consisting of:(i) acopolymer comprising (A) about 40 to about 60 parts by weight of monomerselected from the group consisting of vinyl esters of C₁ to C₈monocarboxylic acids and C₁ to C₁₂ alkyl (meth)acrylates, and (B) about60 to about 40 parts by weight of monomer selected from the groupconsisting of N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide,N-vinylcaprolactam, and mixtures thereof wherein said copolymerstabilizer comprises 100 parts by weight total of the monomers of (i)(A)plus (i)(B); and (C) about 0.5 to about 5 weight percent of a chaintransfer agent based upon the weight of the monomers of (i)(A) plus(i)(B); (ii) a macromonomer comprising the reaction product of thecopolymer of (d)(i) wherein said chain transfer agent selected providessaid copolymer with at least one functional group selected from thegroup consisting of --NH₂, --COOH, --OH, and combinations thereof, withan endcapping agent selected from the group consisting ofisocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenylbenzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidylmethacrylate, and mixtures thereof, wherein at least about 95% of thefunctional groups selected from the group consisting of --NH₂, --COOH,--OH, and combinations thereof, of the copolymer are reacted with theendcapping agent; and (iii) mixtures thereof; (e) about 30 to about 95percent by weight of an organic solvent based upon the total weight of(a) plus (b) plus (c) plus (d) plus (e); and (f) about 0.1 to about 0.5percent by weight of a crosslinker based upon the weight of (a) plus (b)plus (c) plus (d).
 5. An adhesive composition comprising:a dispersioncomprising the polymerization product of a mixture comprising: (a) about10 to about 30 parts by weight of a fluoroalkyl siloxane of the formula##STR7## wherein: R⁹ is independently selected from the group consistingof --CH₂ CH₂ R_(f) and -R⁷, R_(f) is a fluoroalkyl group independentlyselected from the group consisting of C_(m) F_(2m-1) and C_(n)F.sub.(2n+1)-q H_(q), m is an integer ranging from about 1 to about 20;n is an integer ranging from about 1 to about 20; q is an integerranging from about 0 to about 2n; x is an integer of about 11 orgreater; the fluoroalkylsiloxane comprises 10 or greater --CH₂ CH₂ R_(f)groups; the fluoroalkylsiloxane comprises at least 1 R⁷ group; whereinR¹, R², R³, R⁴, R⁵, R⁶, and R⁸ are each independently selected from thegroup consisting of alkyl groups comprising about 1 to about 12 carbonatoms, aralkyl, alkaryl, alkoxy, alkylamino, hydroxyl, fluoroalkyl, andhydrogen; and R⁷ is an organic group having at least two carbon atomswherein at least 1 olefinic moiety is contained within R⁷ ; wherein theratio of R⁷ to --CH₂ CH₂ R_(f) is such that the mole percent of theolefinic moiety content contributed by R⁷ of the fluoroalkyl siloxane isbetween about 0.1 and about 4; (b) about 70 to about 90 parts by weightof free-radically polymerizable monomer, wherein said free-radicallypolymerizable monomer comprises:(i) about 5 to about 15 percent byweight of free-radically polymerizable polar monomer; and (ii) about 85to about 95 percent by weight of free-radically polymerizable non-polarmonomer; wherein said weight percentages of (i) and (ii) are based uponthe total weight of (i) plus (ii); and wherein the total weight of (a)plus (b) equals 100 parts by weight total; (c) about 0.2 to about 0.8parts by weight of a free radical initiator based upon 100 parts byweight total of (a) plus (b); (d) about 3 to about 6 parts by weight ofa stabilizer based upon 100 parts by weight of total of (a) plus (b)wherein said stabilizer has a number average molecular weight rangingfrom about 8000 to about 25,000 and wherein said stabilizer is selectedfrom the group consisting of:(i) a copolymer comprising (A) about 40 toabout 60 parts by weight of monomer selected from the group consistingof vinyl esters of C₁ to C₈ monocarboxylic acids and C₁ to C₁₂ alkyl(meth)acrylates, and (B) about 60 to about 40 parts by weight of monomerselected from the group consisting of N-vinylpyrrolidone, acrylamide,N,N-dimethylacrylamide, N-vinylcaprolactam, and mixtures thereof whereinsaid copolymer stabilizer comprises 100 parts by weight total of themonomer of (i)(A) plus (i)(B); and (C) about 0.5 to about 5 weightpercent of a chain transfer agent based upon the weight of the monomersof (i)(A) plus (i)(B); (ii) a macromonomer comprising a reaction productof the copolymer of (d)(i) wherein said chain transfer agent selectedprovides said copolymer with at least one functional group selected fromthe group consisting of --NH₂, --COOH, --OH, and combinations thereof,with an endcapping agent selected from the group consisting ofisocyanatoethyl methacrylate, alpha, alpha-dimethyl-meta-isopropenylbenzylisocyanate, vinyl azlactone, para(chloromethyl) styrene, glycidylmethacrylate, and mixtures thereof, wherein at least about 95% of thefunctional group(s) selected from the group consisting of --NH₂, --COOH,--OH, and combinations thereof, of the copolymer are reacted the withend-capping agent; and (iii) mixtures thereof; and (e) about 40 to about50 percent by weight of an organic solvent based upon the total weightof (a) plus (b) plus (c) plus (d) plus (e); and (f) about 0.1 to about0.5 percent by weight of a crosslinker based upon the weight of (a) plus(b) plus (c) plus (d).
 6. The adhesive of claim 4 wherein saidcrosslinker is selected from the group consisting of soluble metalsalts, metal complexes, silanes, triazines, aromatic ketone monomers,multifunctional aziridine amides and mixtures thereof.
 7. The adhesiveof claim 5 wherein said crosslinker is selected from the groupconsisting of soluble metal salts, metal complexes, silanes, triazines,aromatic ketone monomers, multifunctional aziridine amides, and mixturesthereof.